This research proposal is concerned with the development of new synthetic methods and applications of the type 2 intramolecular Diels-Alder reaction. The type 2 intramolecular Diels-Alder reaction and the resulting anti-Bredt olefins have found application in organic synthesis. The constraints resulting from the connectivity in the Diels-Alder precursor creates a strong regio- and stereochemical bias in the cycloaddition step. The end result of this bias is the stereoselective synthesis of highly substituted carbocyclic and heterocyclic rings. The utility of this reaction has been demonstrated in recent applications of the type 2 IMDA reaction as a key step in the total synthesis of complex natural products. The proposal contains three sections; 1) the development of asymmetric catalysts for the type 2 IMDA reaction; 2) an exploration of the type 2 intramolecular acyl nitroso Diels-Alder cycloaddition and related heteroatom reactions, and 3) the synthesis and chemistry of bridgehead allyl silanes. The synthetic methods and novel polycyclic structures that will result from this research will enhance the utility of this transformation and provide powerful tools for the synthesis of biologically important compounds.